Abstract
Oleic acid esters of phytosterols (PSs) and triterpene alcohols (TAs), derived from rice bran, were synthesized using lipases under mild conditions. Some lipases, especially from Candida rugosa, type VII, showed very high substrate specificity towards both PSs and TAs, when a mixture of PS and TA (PS/TA mixture) was used as the substrate source. The maximum yield of PS esters was ca. 80 % in each case; however, the maximum yield of TA esters was much lower when the reaction was continued for 7 days. Due to the difficulty in purifying the esters obtained when the PS/TA mixture was used as source of substrate, free PSs and TAs were separated from the PS/TA mixture by silica-gel and reverse-phase chromatography prior to esterification. The pure PSs or TAs were esterified with oleic acid to obtain the corresponding esters with high purity. Differential scanning calorimetric analysis of the resulting esters revealed that their melting points ranged from 7.0 to 42 °C. These values were at least 100 °C lower than those of the free PSs and TAs.
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References
Graf E (1992) Antioxidant potential of ferulic acid. Free Radic Biol Med 13:435–448
Kikuzaki H, Hisamoto M, Hirose K, Akiyama K, Taniguchi H (2002) Antioxidant properties of ferulic acid and its related compounds. J Agric Food Chem 50:2161–2168
Xu Z, Godber JS (1999) Purification and identification of components of γ-oryzanol in rice bran oil. J Agric Food Chem 47:2724–2728
Yasukawa K, Akihisa T, Kimura Y, Tamura T, Takido M (1998) Inhibitory effect of cycloartenol ferulate, a component of rice bran, on tumor promotion in two-stage carcinogenesis in mouse skin. Biol Pharm Bull 21:1072–1076
Peterson DW (1951) Effect of soybean sterols in the diet on plasma and liver cholesterol in chicks. Proc Soc Exp Biol Med 78:143–147
Pollak OJ (1953) Reduction of blood cholesterol in man. Circulation 7:702–706
Folmer BM (2003) Sterol surfactants: from synthesis to applications. Adv Colloid Interface Sci 103:99–119
Hoppe U, Larsson K (1981) Water-in-oil emulsions -a study of wool-wax alcohol-systems. J Dispersion Sci Technol 2:433–441
Puglia C, Bonina F (2008) In vivo spectrophotometric evaluation of skin barrier recovery after topical application of soybean phytosterols. J Cosmet Sci 59:217–224
Akihisa T, Yasukawa K, Yamaura M, Ukiya M, Kimura Y, Shimizu N, Arai K (2000) Triterpene alcohol and sterol ferulates from rice bran and their anti-inflammatory effects. J Agric Food Chem 48:2313–2319
Chang RC, Chou SJ, Shaw JF (1994) Multiple forms and functions of Candida rugosa lipase. Biotechnol Appl Biochem 19:93–97
Fernholz E, MacPhillamy HB (1941) Isolation of a new phytosterol: campesterol. J Am Chem Soc 63:1155–1156
Hircher HW, Rosenstein FU (1973) Isolation of brassicasterol from steam deodorizer distillate of rapeseed oil: some properties of its acetate tetrabromide and its reduction to 22, 23-dihydrobrassicasterol. Lipids 8:453–458
Kircher HW, Rosenstein FU (1973) Purification of sitosterol. Lipids 8:97–100
Nishioka I, Ikekawa N, Yagi A, Kawasaki T, Tsukamoto T (1965) Studies on the plant sterols and triterpenes. ii. separation of stigmasterol, β-sitosterol and campesterol, and about so-called “γ-sitosterol”. Chem Pharm Bull (Tokyo) 13:379–384
Li J, Ho C-T, Li H, Tao H, Tao L (2000) Separation of sterols and triterpene alcohols from unsaponifiable fractions of three plant seed oils. J Food Lipid 7:11–20
Bentley HR, Henry JA, Irvine DS, Spring FS (1953) Triterpene resinols and related acids. Part XXVIII. The non-saponifiable fraction from strychnos nux-vomica seed fat: the structure of cycloartenol. J Chem Soc 3673–3678
Starratt AN (1966) Triterpenoid constituents of Euphorbia cyparissias. Phytochemistry 5:1341–1344
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This study was financially supported by Project Support R&D of the Innovative Industry Technology, Wakayama Prefecture, Japan.
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Kobayashi, T., Ogino, A., Miyake, Y. et al. Lipase-Catalyzed Esterification of Triterpene Alcohols and Phytosterols with Oleic Acid. J Am Oil Chem Soc 91, 1885–1890 (2014). https://doi.org/10.1007/s11746-014-2531-1
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DOI: https://doi.org/10.1007/s11746-014-2531-1